Preparation of n-alkanoxy ammonium halides



3,183,236 PREPARATIUN F N-ALKANOXY AMIVIONIUM HALIDES Denys Cook and Stephen Joseph Kuhn, Sarnia, Ontario, Canada, assignors to The Dow Chemical Company, Midland, Mich, a corporation of Delaware 7 N0 Drawing. Filed Feb. 12, 1962, Ser. No. 172,819 6 Claims. (Cl. 260-29415) The present invention relates to a novel class of organic compounds and more particularly relates to a method of preparation and to a novel class of organic compounds having the formula Z+OA (I) wherein Z represents an ammonium radical having one of the formulas R R N+; l I -q N X?- R A represents a radical having one of the formulas o 0 7 LL II R; -fi-R' wherein R represents an alkyl radical having from 1 to carbon atoms, R represents an organic radical the residue of an acyl or sulfonyl halide, and X represents a halogen having an atomic number from 17 to 35, inclusive. These compounds have been found useful having insecticidal and bactericidal properties.

The novel compounds can be prepared by reacting a tertiary amine oxide having one of the formulas wherein each of the symbols R, and R, have the significance aforesaid, in the presence of an inert solvent for the reactants but which is a non-solvent for the products, at a temperature from about 10 C. to about 40 C. The insoluble product can be recovered in conventional manner such as filtration.

The tertiary amine oxides which can be employed in accordance with the present invention are those having the general Formulas II, III or IV. Some of such compounds are, pyridine N-oxide, 4-picoline N-oxide, quinoline N-oxides, acridine N-oxides, pyrazine N-oxide, trimethylamine N-oxide, triethylamine N-oxide, tripropylamine N-oxide, tributylamine N-oxide, tripentylamine N-oxide, their isomers and the like.

The carbonyl chlorides which can be employed in accordance with the present invention are those having the general Formula V, the aliphatic acyl chlorides, the arylacyl chlorides, their halo analogs, and the like such as acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride, benzoyl chloride, phenacctyl chloride United States Patent the group consisting of 'diethyl ether.

3,133,236 Patented May 11, 1965 "ice and the like; as well as the diphenyl alkanoyl chlorides, and the.N,N-diphenyl carbamoyl chloride.

The sulfonyl chlorides, which can be employed are those having the general Formula VI, benzene sulfonyl chloride, naphthalene sulfonyl chloride, butyl sulfonyl chloride and the like.

The following examples are illustrative of the present invention but are not to be construed as limiting.

Example 1 Example 2 9.5 grams (0.1 mol) of pyridine-N-oxide dissolved in 200 ml. acetone and 300 ml. diethyl ether added. 12.3 grams (0.1 mol) acetyl bromide added slowly to the cooled solution of the N-oxide (0 C.). The white pre cipitate was filtered and washed taking precautions to exclude atmospheric moisture. Almost quantitative yield of N-acetoxy pyridinium bromide resulted.

In the manner of Example 2 substituting benzene sulfonyl chloride for acetyl bromide there was obtained l-phenyl sulfonyloxy) pyridinium chloride having the formula -o-sol- Tc1- The novel compounds of the present invention have been tested and found to be usefulas the sole active ingredients in insecticidal and bactericidal compositions. In representative operations 0.05 percent by weight of l-(diphenylcarbamoloxy) pyridinium chloride gave percent kill of Staphyloccocus aureus, Aspergillus terreus, Pullulm'ia pullulanu, and Rhizopus nigricans, when ap plied to a dextrose-nutrient agar inoculated with colonies of the named organisms. Representative of the insecticidal properties was the 100 percent kill of southern army worm when sprayed on infested plants to the point of run off as aqueous solutions containing 500 parts of toxicant per million parts or" water. a

We claim: l. A compound having the formula Z+- O-A wherein Z represents an ammonium radical selected from A 0 1 A represents a radical selected from the group c0nsist- References Cited by the Examiner mg of Klingsberg: Pyridine and Its Derivatives, Part II,

0 0 pp. 125-8 (Interscience) (1961). .lL and g Culvenor: Reviews of Pure and Applied Chemistry,

I 5 vol. 3, N0. 2, pp. 105-109 (1953).

Krohnke et a1.: Ben, vol. 703, pp. 864-78 (1937). wherem R represents alkyl havmg from 1 to 5 carbon Babcock et al.: J.A.C.S., vol. 55, pp. 2949-8 1933 atoms, R represents a member selected from the group Doering et 1 LACS 1 73 2104 9 195 consisting of y p y p y y dlphenyl, and Klages et aL: Annalen, vol. 607, pp. 3545 1957).

p y amino, and having 110 more h n 2 car n 10 Chemical Abstracts, Decennial Index, 1917-1926, atoms, and X represents a halogen having an atomic 5602, number from 17 to 35.

2. N(N,N-diphenyl carbamoxy) pyridinium chloride. IRVING MARCUS, Primary Examiner.

3. N(benzenesulfoxy) pyridinium chloride.

4. N'(N,N-dipheny1 carbam0Xy)-4-rnethyl pyridiniurn 15 3" RIZZO WALTER chloride.

5. N-acetoxy pyridinium bromide.

6. N-(3,4-dichl0robenzoxy) pyridiniurn chloride.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,183,236 May 11, 1965 Denys Cook et a1.

It is hereby certified that error appears in the above numbered patent reqliring correction and that the said Letters Patent should read as cor-rectedbelow.

Column 3, lines 3 to 6, the second formula should appear as shown below instead of as in the patent:

O L' R Signed and sealed this 28th day of September 1965.

(-SEAL) Attcst:

ERNEST W. SWIDER EDWARD J. BRENNER Altcsting Officer Commissioner of Patents 

1. A COMPOUND HAVING THE FORMULA 